Silicon nitride deposition method

ABSTRACT

A silicon nitride deposition method includes providing a substrate surface. Silicon is predeposited on at least a portion of the surface. After predeposition of the silicon, silicon nitride is deposited. The substrate surface may include one or more component surfaces and when at least a monolayer of silicon is predeposited thereon silicon nitride nucleation at the substrate surface is performed at a substantially equivalent rate independent of the different component surfaces.

This application is a continuation of application Ser. No. 08/955,793,filed Oct. 22, 1997, which is a continuation of application Ser. No.08/655,728, filed May 30, 1996, issued as U.S. Pat. No. 5,939,333.

FIELD OF THE INVENTION

The present invention relates to the fabrication of integrated circuitdevices. In particular, the present invention pertains to methods forthe deposition of silicon nitride in the fabrication of integratedcircuits and devices resulting from such methods.

BACKGROUND OF THE INVENTION

Surface properties play an important role in the initial growth of filmsin thin-film processes. The increasing need for sophisticated filmpreparation processes, including epitaxial growth, selective growth,trench filling, etc., requires that the surface be uniform and welldefined. Ideally, surface preparation techniques should be optimized foreach particular film deposition process.

In particular, especially for deposited thin-films, the surface statebefore deposition directly impacts the interface properties between thesurface and the thin film deposited. For example, different wafersurfaces, such as tetraethylorthosilicate (TEOS), borophosphosilicateglass (BPSG), or silicon, exhibit different nucleation and averagedeposition rates when silicon nitride is deposited thereon; however,once a uniform layer of nitride is convering the entire surface, theinstantaneous deposition rate should be independent of the originalsurface. Further, for example, when silicon is exposed to air, nativeoxide is formed on the surface of silicon which may decrease the nitridedeposition rate and inhibit the proper termination of silicon bonds atthe silicon surface when a silicon nitride thin film surface isdeposited thereon. The affected interface properties may degrade theisolation performance or dielectric quality of silicon nitride filmsdeposited on the various surfaces.

Silicon nitride (Si₃N₄) deposition is important to the fabrication ofintegrated circuits because silicon nitride films act as diffusionbarriers and have unique dielectric qualities. For example, high-qualitydielectrics formed using silicon nitride films are used in thefabrication of MOSFET gates, memory cells, and precision capacitors. Theinterface between the substrate upon which the silicon nitride isdeposited and the silicon nitride film, at least in part, defines theisolation and dielectric characteristics of the devices utilizing thesilicon nitride film.

In a conventional silicon nitride deposition method 10 as represented inFIG. 1 upon a silicon surface (including single crystal, poly,epitaxial, etc.), the surface upon which the silicon nitride layer is tobe deposited is normally pretreated such as by removing the native oxideusing HF solutions and/or HCL solutions. A film of silicon nitride isthen deposited on the pretreated surface such as by the reaction ofsilane with ammonia. Unless the pretreatment and silicon nitridedeposition are performed in a cluster tool for controllingcontamination, some native oxide may be present on the surface when thesilicon nitride deposition is performed. The presence of native oxidedegrades device performance and although the use of cluster toolsreduces the native oxide growth, cluster tools reduce throughput ofwafers and are generally more costly to operate as compared to standardprocessing equipment, such as conventional deposition reactors.

Moreover, as mentioned above, different nucleation and deposition ratesoccur for the deposition of silicon nitride on different wafer surfaces,such as TEOS, BPSG, or silicon. This leads to different or degradedelectrical characteristics of the devices fabricated using a siliconnitride deposited layer on different wafer surfaces. In addition, whensilicon nitride is deposited, an incubation time occurs at the start ofthe deposition process wherein there is no apparent deposition ofsilicon nitride on the wafer surface. Such differing nucleation anddeposition rates and also the incubation period result in degradedelectrical characteristics of the semiconductor devices beingfabricated.

For the reasons indicated above and for other reasons which will becomeapparent from the detail below, improved methods of forming siliconnitride films are needed to improve the characteristics of thesemiconductors devices fabricated, and also to reduce the cost andincrease the throughput for fabricating such devices.

SUMMARY OF THE INVENTION

The method in accordance with the present invention is an improvedmethod of forming silicon nitride films to improve the characteristicsof semiconductor devices fabricated using silicon nitride films. Suchmethods may be performed at reduced cost and with increased throughputrelative to other methods, such as with the use of cluster tools. In oneembodiment, the method is for use in forming a memory cell dielectric ofan integrated circuit device. The method includes providing a substratesurface of a memory cell including a silicon based electrode surface.Silicon is predeposited on at least the electrode surface of thesubstrate surface after which a silicon nitride layer is depositedthereon. Using the predepostion of silicon, an incubation time for thestart of silicon nitride nucleation at the electrode surface isdecreased relative to the incubation time for the start of siliconnitride nucleation when silicon nitride is deposited withoutpredeposition of silicon on the electrode surface.

In one embodiment of this method, the predeposition step includes thestep of predepositing at least a monolayer of silicon on at least theelectrode surface. Further, the predeposition step may include the stepof predepositing the silicon using one of silane, disilane, silicontetrachloride, dichlorosilane, trichlorosilane and the substrate surfacemay include one or more different surface types includingtetraethylorthosilicate, borophosphosilicate glass, silicon,polysilicon, other doped silicon or polysilicon surfaces, other dopedoxides, thermal silicon dioxide, chemical vapor deposited silicondioxide, and plasma enhanced chemical vapor deposited silicon dioxide.The silicon nitride nucleation at the substrate surface having siliconpredeposited thereon is performed at a substantially equivalent rateindependent of the surface type.

In another method of the present invention, silicon nitride depositionis performed by providing a substrate surface including one or moredifferent component surfaces. At least a monolayer of silicon ispredeposited on the one or more component surfaces of the substratesurface resulting in a substantially native oxide free uniformpredeposited silicon substrate surface. A silicon nitride layer is thendeposited on the predeposited silicon substrate surface after thesilicon predeposition.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a general flow diagram of a conventional silicon nitridedeposition method;

FIG. 2 is a more detailed flow diagram of the conventional siliconnitride deposition method of FIG. 1;

FIGS. 3A-3C are illustrations of various embodiments of memory cellshaving a dielectric formed in accordance with the method of the presentinvention;

FIG. 4 is a general flow diagram of a silicon nitride deposition processin accordance with the present invention including pretreatment;

FIG. 5 is a more detailed flow diagram of one particular embodiment ofthe silicon nitride deposition step of the process illustrated in FIG. 4using a silicon predeposition process;

FIG. 6 is a more detailed flow diagram of another embodiment of thesilicon nitride deposition step of the process illustrated in FIG. 4using a nitridation process prior to conventional deposition of asilicon nitride layer;

FIG. 7 is an illustrative diagram of an LPCVD nitride system for use inthe silicon nitride deposition step of the process illustrated in FIG. 4in accordance with the present invention;

FIG. 8A is a general illustrative top view diagram of an LPCVD nitridecluster tool for use in performing he silicon nitride deposition processillustrated in FIG. 4 in accordance with the present invention; and

FIG. 8B is a general illustrative front view diagram of the LPCVDnitride cluster tool of FIG. 8A, excluding the input/output module, foruse in performing the silicon nitride deposition process illustrated inFIG. 4 in accordance with the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

A conventional silicon nitride deposition process 10 for depositing asilicon nitride film is generally represented in the flow diagram ofFIG. 1 and in further detail in the flow diagram of FIG. 2. Theconventional method 10 generally includes a pretreatment or cleaning ofthe surface onto which the silicon nitride film or layer is to bedeposited or grown (block 12) and includes the formation of the siliconnitride layer (block 14), such as by chemical vapor deposition (CVD).

The surface to be pretreated and onto which the silicon nitride layer isto be deposited may include different wafer surfaces of thesemiconductor device being fabricated. For example, the wafer surfacemay include one or more of tetraethylorthosilicate (TEOS),borophosphosilicate glass (BPSG), silicon, polysilicon, other dopedsilicon or polysilicon surfaces, other doped oxides, thermal silicondioxide, chemical vapor deposited (CVD) silicon dioxide, plasma enhancedCVD (PECVD) silicon dioxide, or any other film or surface upon whichsilicon nitride would be deposited in the fabrication of semiconductordevices.

The pretreatment (block 12) of the wafer surface in the conventionalmethod may include any number of cleaning steps. Ultra clean water withvery low ionic content may be utilized to perform one or more rinsesduring the cleaning process. Water having a very low ionic content has aresistivity of about 15 to 18 Mohms-cm.

A suitable pretreatment (block 12) may include a wet cleaning of thesurface performed by immersing a wafer in an appropriate liquidsolution, by spraying the wafer surface with the liquid solution, or byexposing the surface to a cleaning vapor. Such a wet cleaning may beaccompanied with agitation or scrubbing such as by a brush or sonicpower.

Wet cleaning may include cleaning the surface with an RCA clean as isknown to one skilled in the art utilizing hydrogen peroxide (H₂O₂).However, typically, to remove native oxide from silicon wafer surfaces,an immersion in an HF solution or treatment by an HF vapor is used. Theimmersion or treatment may be for a period of time limited to, forexample, 15 seconds. Further, such treatment or immersion may berepeated as necessary. Native oxide removal, for example, with respectto a silicon surface, is evidenced by the change of the surface from ahydrophilic oxidized surface to a hydrophobic bare silicon surface.

As shown by block 12 of FIG. 2, in a conventional pretreatment process,native oxide is removed by an HF clean, such as by immersion in an HFsolution, or by HF vapor treatment, as represented by block 112. The HFcleaned surface is then rinsed in deionized water (block 113) and dried(block 114) as is known to one skilled in the art to result in ahydrophobic oxide free surface. Other cleaning processes may be utilizedin addition to those described above and are clearly contemplated inaccordance with the scope of the present invention as described in theaccompanying claims. For example, some other pretreatment or cleaningprocesses may include the use of NH₄F solution, NH₄F/HF solution orbuffered oxide etch (BOE), or any other cleaning solution known to oneskilled in the art that provides a hydrophobic oxide free surface.

Conventional methods are then typically used for forming a siliconnitride layer on the oxide free wafer surface as represented by block 14in FIG. 1. Such conventional methods may include growing a siliconnitride film on silicon by reacting nitrogen or a nitrogen compound,such as ammonia (NH₃) with surface silicon atoms at elevatedtemperatures, typically 900° C. to 1300° C. As is known to one skilledin the art, a silicon nitride layer or film can also be formed ordeposited on wafer surfaces utilizing CVD techniques. For example, afilm of silicon nitride can be deposited by reacting silane with ammoniaat about 700° C. to 900° C. and at atmospheric pressure. The depositionrate increases rapidly with temperature. While the rate of deposition at700° C. may be less than 1 nm/min, it may increase to 100-200 nm/min at900° C. The deposition rates will vary depending upon various conditionsof the deposition as is well known to one skilled in the art.

Further, a conventional low pressure chemical vapor deposition (LPCVD)process may be used for depositing the silicon nitride film. The LPCVDsilicon nitride process may include, for example, the reaction ofdichlorosilane (DCS) and ammonia (NH₃) at a temperature of about 700° C.to 800° C. to deposit the silicon nitride film. Typical silicon tonitrogen ratios in such films range from 0.7 to 1.1 and the filmsdeposited contain bonded hydrogen in the form of Si—H and N—H bonds.Moreover, additional conventional silicon nitride deposition processesare also suitable for deposition of silicon nitride. For example, suchprocesses may include chemical physical deposition processes, plasmaenhanced chemical vapor deposition processes, and rapid thermal chemicalvapor deposition processes.

The preferred conventional method for deposition of the silicon nitridefilm is LPCVD of silicon nitride. The preferred conditions for LPCVDinclude a temperature in the range of about 650° C. to about 800° C., apressure in the range of about 50 mTorr to about 700 mTorr, and with anNH₃:DCS ratio in the range of about 3:1 to about 10:1. However, althoughLPCVD and these conditions are preferred, other deposition methods andconditions also produce suitable silicon nitride films.

With respect to thin silicon nitride films, such as those deposited by aprocess using conventional hot wall LPCVD furnaces, different nucleationrates and average deposition rates have been shown to occur on differentwafer surfaces. Surfaces exhibiting such different rates include but arenot limited to one or more of tetraethylorthosilicate (TEOS),borophosphosilicate glass (BPSG), silicon, polysilicon, other dopedsilicon or polysilicon surfaces, other doped oxides, thermal silicondioxide, chemical vapor deposited (CVD) silicon dioxide, and plasmaenhanced CVD (PECVD) silicon dioxide. Further, deposition of siliconnitride on each of these surfaces also includes an incubation time atthe start of the deposition where there is no apparent deposition ofsilicon nitride. This is particularly apparent where a cluster tool isnot utilized, as described further below, and native oxide is grown onthe silicon surfaces due to transfer through atmosphere from, forexample, an HF vapor module to the LPCVD reactor. Such an incubationtime may be as long as several minutes for some surfaces, although theincubation time is highly dependant on the deposition conditions whichmay vary. Thin silicon nitride films are typically 60 to 200 angstromsand more generally may include films of 500 angstroms or less. Moreover,such films may be less than 60 angstroms, such as 40 angstroms and less.Further, the present invention may provide benefit for thicker films,for example, 500 angstroms and above. However, the initial incubationtime has less overall effect with respect to thicker films and thus thepresent invention may provide less overall benefit, i.e. the percentageof total deposition time taken up by the incubation time is less forthicker films.

In the conventional silicon nitride formation process 10 shown in FIG.1, the process of pretreatment (block 12) of the wafer surfaces may beperformed in situ with respect to the silicon nitride formation step(block 14). For example, a vacuum loadlock cluster tool, such asillustrated in FIG. 8A and 8B, may be utilized to perform thepretreatment (block 12), such as an HF vapor clean in an HF vapor module306, and then the wafers are transferred to an LPCVD module 302 forsilicon nitride deposition by a wafer transfer module 308 withoutexposure to air to prevent native oxide formation. In such a case, theincubation time for formation of the silicon nitride layer in the LPCVDmodule will likely be zero.

As shown by the detail flow diagram of FIG. 2, the conventionalformation of the silicon nitride layer (block 14) can be performed, forexample, by conventional LPCVD in the following manner as described withreference to FIG. 7, after the surface has been pretreated. The wafers220 would be transferred to an LPCVD nitride deposition system 200 froma pretreatment unit (not shown). The wafers 220 would be positioned inthe deposition chamber 204 of the system 200 via the door 214 and wouldbe sealed in the chamber 204 as the sealing surfaces 212 come intocontact. The heating elements 202 of the system are utilized to bringthe temperature in the range of about 700° C. to 800° C.

Utilizing pump 206 of the system 200, the system is pumped down to apressure of about 10 mTorr or less (block 115) after which an N₂ purge(block 116) is performed to clear out the deposition chamber 204.Although N₂ is preferred for the purge, any other inert gas is suitablefor use. Following the N₂ purge, the system is pumped down again to apressure of about 10 mTorr or less (block 117) after which an NH₃prepurge (block 118) is performed during which the pressure is in therange of about 50 mTorr to about 700 mTorr. Plumbing to the chamber 204for providing DCS, NH₃, and N₂ is generally designated by arrows 208 and210 as is well known to those skilled in the art. For example, DCS andN₂ are provided by plumbing 208 and NH₃ and N₂ are provided by plumbing210.

After the NH₃ prepurge (block 118), the DCS/NH₃ nitride deposition(block 119) is performed in accordance with the conventional LPCVDprocess and conditions described above. Following the silicon nitridelayer being deposited (block 119), an NH₃ post purge (block 120) isperformed during which the pressure is in the range of about 50 mTorr toabout 700 mTorr and then the system is pumped down (block 121) to apressure of about 10 mTorr or less. The deposition chamber is thenvented (block 122) to atmosphere using N₂.

In accordance with the present invention as will be described withreference to FIGS. 2-8, a predeposition process is performed prior todepositing or growing the silicon nitride layer or film by theconventional LPCVD nitride deposition. As represented by the generalflow diagram of FIG. 4, the silicon nitride deposition process 20 inaccordance with the present invention includes pretreatment of a waferor substrate surface as represented by block 22 and deposition of asilicon nitride layer utilizing the predeposition step or process (block24).

The wafer surface, or also referred to herein as the substrate surface,to be pretreated as represented by block 22 includes surfaces such asthose surfaces of the various memory cells shown in FIGS. 3A-3C uponwhich a thin silicon nitride dielectric layer is deposited. The surfacemay include one or more of any one of the different types of surfaces asdescribed above, including but not limited to wafer surfaces such astetraethylorthosilicate (TEOS), borophosphosilicate glass (BPSG),silicon, polysilicon, other doped silicon or polysilicon surfaces, otherdoped oxides, thermal silicon dioxide, chemical vapor deposited (CVD)silicon dioxide, plasma enhanced CVD (PECVD) silicon dioxide, or anyother film or surface upon which silicon nitride would be deposited inthe fabrication of semiconductor devices. For example, the substratesurface may include a silicon surface portion, a TEOS surface portion, afield oxide portion or a polysilicon portion as shown in FIGS. 3A-3C tobe described further below. Because the substrate surface may includedifferent types of surfaces, it is important that the nitride nucleationand deposition rates of silicon nitride be substantially equivalent forthe different surfaces. Such uniform nucleation and deposition ratesbetween the different wafer surfaces result in improved electricalcharacteristics for the semiconductor devices fabricated.

The pretreatment of the substrate surface (block 22) in accordance withthe present invention is performed in a conventional manner as describedabove with reference to FIG. 1. For example, in addition to the HFimmersion and the preferred HF vapor treatment as described previously,native oxide may be removed using a buffered HF solution, such asHF:NH₄F. The pretreatment may be performed in one or more treatment orimmersion steps and further one or more rinsing steps in deionized watermay be utilized. The pretreatment (block 22) terminates the siliconsurface with a monolayer of hydrogen or, in other words, results in ahydrogen terminated surface. It will be readily apparent to one skilledin the art that many other pretreatment or cleaning processes may beused without departing from the present invention as described in theaccompanying claims. For example, any pretreatment method, althoughpreferably an HF vapor clean, may be used which results in a nativeoxide free surface.

The deposition of the silicon nitride layer using a predepositionprocess, as represented generally by block 24 in FIG. 4, may beperformed in a number of different manners as is apparent from thedifferent embodiments shown in FIGS. 5 and 6. In the embodiment of FIG.5, the predeposition process (block 25) includes predepositing siliconprior to the conventional silicon nitride deposition step 146. In theembodiment of FIG. 6, the predeposition process (block 26) includesnitridating a silicon based surface, for example polysilicon, prior tothe conventional silicon nitride deposition. With the use of thepredeposition process, the nucleation rate, i.e. the number ofnucleation sites, is increased at the interface between the substratesurface and the silicon nitride layer deposited thereon by conventionalmethods. Such an increase in nucleation at the interface provides forimproved electrical characteristics, for example, dielectriccharacteristics.

As shown in the flow diagram of FIG. 5, the deposition of the siliconnitride layer using the predeposition process (block 24) in accordancewith the present invention is performed in substantially the same manneras described with respect to FIG. 2 with the addition of thepredeposition step 25. Therefore, the following description withreference to FIG. 5 shall be substantially limited to the predepositionstep 25. The substrate surface, as described previously, may include oneor more of tetraethylorthosilicate (TEOS), borophosphosilicate glass(BPSG), silicon, polysilicon, other doped silicon or polysiliconsurfaces, other doped oxides, thermal silicon dioxide, chemical vapordeposited (CVD) silicon dioxide, plasma enhanced CVD (PECVD) silicondioxide, or any other film or surface known to one skilled in the artupon which silicon nitride would be deposited in the fabrication ofsemiconductor devices.

As shown in FIG. 5, after the pump down 142 the predeposition step(block 25) includes predepositing silicon (block 143) and then pump down(block 144) to a pressure of about 10 mTorr or less. The predepositionprocess is then followed by the NH₃ prepurge (block 145) and theremainder of the steps as set forth in the description with reference toFIG. 2. The predeposited silicon film gives the wafer surface orsurfaces a uniform silicon “appearance” at the start of the siliconnitride nucleation and deposition.

The predeposition of the silicon as represented by block 143 may beperformed using silicon hydrides or silanes such as dichlorosilane (DCS,SiH₂Cl₂), silane (SiH₄), disilane (H₃SiSiH₃), trichlorosilane (TCS,SiHCl₃), or any other silicon precursor known to one skilled in the art.The thin silicon film predeposited (block 143) generally includes amonolayer or more in thickness. Preferably, the predeposition step(block 143) is performed using one of DCS, silane, or disilane, althoughDCS and silane are preferred over the others. Use of DCS may bebeneficial as most LPCVD nitride deposition systems have DCS plumbed tothe deposition chamber.

The predeposition using silane may be carried out at a temperature inthe range of about 500° C. to about 800° C. and at a pressure in therange of about 50 mTorr to about 500 mTorr. On the other hand, thepredeposition method using DCS to predeposit the silicon may beperformed at a temperature in the range of about 900° C. to about 1000°C. and at a pressure in the range of about 50 mTorr to about 500 mTorr.Dichlorosilane is provided to the interior chamber 204 of an LPCVDsystem, such as by plumbing 208 of system 200 shown in FIG. 7; theinterior chamber having located therein the wafers 220 including thesurfaces upon which the silicon nitride layer is to be deposited.

The preferred method of predepositing the silicon includes the use ofDCS because a standard LPCVD silicon nitride deposition system willtypically already have DCS plumbed to the system. Further, the DCS tosilicon deposition is a relatively slow reaction which can improve theprocess control needed to make the predeposited silicon at least amonolayer.

With respect to the process using the predeposition of silicon prior tothe conventional silicon nitride deposition, several distinct advantagesresult therefrom. For example, with use of the predeposited silicon onthe substrate surface or surfaces, a uniform silicon appearance isapparent at the time of the silicon nitride deposition. As such, thenitride nucleation and deposition rate of the silicon nitride upon thepredeposited silicon is substantially the same and not dependant onwhether the surface or surfaces are TEOS, silicon, BPSG, etc.

In addition, silicon nitride nucleation occurs faster with the use ofthe predeposited silicon than when no predeposition method is utilized.Such faster nucleation occurs because there is virtually no incubationtime at the start of the silicon nitride deposition method. The thinsilicon predeposited film is similar in nature to the silicon surfacethat would be formed when the silicon is precleaned insitu in a clustertool as described further below. Therefore, when using a cluster tool,the advantage of faster silicon nitride nucleation may not be apparentbecause there is virtually no incubation period as no native oxide isallowed to form between HF preclean and silicon nitride deposition.However, the predeposition process used with a cluster tool stillprovides the benefit of uniform nucleation and substantially equivalentdeposition rates of the silicon nitride on different wafer surfaces orfilms.

Further, the semiconductor devices fabricated with the silicon nitridedeposition method according to the present invention has improvedelectrical characteristics due to uniform nucleation, substantiallyequivalent deposition rates between different wafer surfaces, and fasternucleation. Such electrical characteristics include, for example, higherbreakdown voltage and greater oxidation resistance compared to siliconnitride deposited by conventional LPCVD techniques. In conventionalsilicon nitride deposition processes where a predeposition is notutilized, different or degraded electrical characteristics result fromthe differences in the nitride thickness deposited on adjacent surfaces.Such differences are especially apparent between a conductor (i.e.silicon) and an insulator (i.e. TEOS). Therefore, the relatively thinnitride deposited at, for example, a silicon/TEOS edge can result indegraded electrical properties at that edge and for the resultingdevices fabricated therewith. The predeposition processes reduce suchthickness differences and therefore alleviate such problems.

As shown in the flow diagram of FIG. 6, the deposition of the siliconnitride layer using the predeposition process (block 24) in accordancewith the present invention is performed in substantially the same manneras described with respect to FIG. 2 with the addition of the nitridationstep 26. Therefore, the following description with reference to FIG. 6shall be substantially limited to the nitridation step 26. The substratesurface which is nitridated prior to conventional thin silicon nitridedeposition is preferably a silicon, polysilicon, or other doped siliconor polysilicon surface.

As shown in FIG. 6, after the pump down 162, the predeposition process(block 26) is performed. The predeposition process (block 26) includesnitridation of the silicon based surface (block 163) and then pump down(block 164) to a pressure of about 10 mTorr or less. The predepostionprocess (block 26) is then followed by the NH₃ prepurge (block 165) andthe remainder of the steps as set forth in the description withreference to FIG. 2.

The nitridation of the silicon based surface (block 163) is performed ina dimethylhydrazine (DMH) (H₂N—N(CH₃)₂) or ammonia (NH₃) atmosphere at atemperature in the range of about 400° C. to about 600° C. and at apressure in the range of about 1 mTorr to about 10 mTorr. For example,nitride deposition is initiated by introducing a stream of DMH or NH₃into an LPCVD system, such as by plumbing 208 into the depositionchamber 204 of the system 200 as shown in FIG. 7 which has the waferstherein for exposure of the hydrogenated wafer surfaces to the stream.The result of the nitridation is that nitrogen atoms are bound uniformlywith three silicon atoms. Below 500° C., the surface coverage should bea monolayer of silicon nitride, independent of temperature, although thetime required to achieve the monolayer increases as temperaturedecreases. On the contrary, at 550 to 600° C., the surface exceeds amonolayer and at 600° C., the surface coverage may approach a doublelayer of silicon nitride. Suitable nitridation of the silicon basedsurfaces results in less than three monolayers of silicon nitrideformation and preferably less than a double layer of silicon nitride.Beneficial nitridation prior to the conventional silicon nitridedeposition may even be less than a monolayer. The time period necessaryfor nitridating the surface is dependent on the other conditions usedfor the deposition and the desired thickness.

Because DMH is a derivative of hydrazine (H₂NNH₂), which is veryreactive, DMH causes nitridation of the hydrogen terminated siliconsurface without the need for the desorption of hydrogen. Therefore, thenitridation rates using DMH are higher than those using NH₃. Alsobecause of the high reactivity, surface contamination during nitridationwith DMH is reduced because, for example, bare silicon surfaces, whichare susceptible to contamination, are not required for nitridation.

Further, because DMH contains carbon atoms, there is a possibility ofincorporating carbon into the silicon surfaces above certaintemperatures. Therefore, it is preferable to nitridate the surface at atemperature in the range of about 400° C. to about 500° C. to avoidcarbon incorporation in the silicon surface.

The passivation of a surface with, for example, a monolayer of N atomsimproves the interface characteristics between the surface and thesilicon nitride layer deposited thereon. This is of particularimportance in cell dielectrics for memory cells, such as the memorycells shown in FIGS. 3A-3C. The electrical characteristics of theinterface and the cell dielectrics are dependant upon the nucleationrate, i.e. the number of nucleation sites, which are increased with thepredepostion process to provide an improved interface.

After the predeposition of silicon (block 25) or the nitridation of thesurface (block 26) are performed and pump down is performed, aconventional silicon nitride process as describe above with reference toFIG. 1 is performed to complete the silicon nitride deposition process20 as shown in FIG. 4. The silicon nitride process 20 can be carried outusing any of the methods previously described and using different typesof reactors, such as LPCVD reactors, CVD reactors, single waferreactors, etc.

Preferably, the predepositions (blocks 25 and 26) and conventionalsilicon nitride deposition as shown in FIGS. 1, 5, and 6 are carried outusing a LPCVD nitride system as shown in FIG. 7 or a cluster tool 300 asgenerally illustrated in FIGS. 8A and 8B. The predepositions andconventional silicon nitride depositions have been previously describedwith reference to FIGS. 1, 5, and 6 using the LPCVD nitride system 200of FIG. 7. The following, therefore, is only a general description ofthe process 20 of FIG. 4 utilizing the cluster tool 300 with referenceto FIGS. 8A and 8B.

The cluster tool illustrated in FIG. 8A and 8B, includes an LPCVD module302, an HF etch module 306, a wafer transfer module 308, and aninput/output module 304. The generalized top view of FIG. 8A shows thegeneral relative position of the modules relative to one another withthe wafer transfer tool 310, such as a robotic tool, being capable oftransferring the wafers between the various modules without exposure toatmosphere and thus without the growth of native oxide between processessuch as HF vapor clean and nitride deposition. The wafers 356 are inputand output through door 312 of input/output module 304 which is the onlymodule that is taken between atmosphere and vacuum by pump 336 duringthe process. The wafers 356 are transferred between the various modulesunder vacuum by the wafer transfer tool 310 via doors 314, 316, and 318.The portions of the modules under vacuum are shown more clearly in FIG.8B which is generally a view from the front of the system with theinput/output module removed. Such portions under vacuum include thelower portion of the LPCVD module 302, the lower portion of the HF etchmodule 306, and the wafer transfer module 308; the vacuum conditionsbeing provided by pumps 330, 332, and 334. The proper conditions for thevarious processes in the module are provided, at least in part, by thepumps 344 and 346 and the heating elements associated with the variouschambers (not all shown). Such cluster tools are generally known to oneskilled in the art and any cluster tool configuration for providingtransfer from module to module without exposure to atmosphere issuitable for use in performing the method of the present invention.

Generally, when using the cluster tool, the wafers are input via theinput/output module 304 which is then evacuated. The wafer transfer toolthen moves the wafers to the HF etch module 306 for performing an HFvapor clean in chamber 350 as described previously with reference toFIG. 1 to remove native oxide from the substrate surface. The wafertransfer tool 310 then transfers the pretreated wafers under vacuum andwithout the possibility of native oxide growth to the LPCVD module 302for predeposition in accordance with the present invention as describedpreviously with reference to FIGS. 5 and 6, and also conventionalsilicon nitride deposition as described previously also with referenceto FIGS. 5 and 6 and, in addition, with reference to FIG. 1.

Use of the cluster tool is contrasted with the process 20 that is notperformed insitu. For example, the silicon nitride process 20 of FIG. 4may be carried out by performing the pretreatment or cleaning process,such as an HF preclean, in a HF vapor chamber. The pretreated waferswould then be transferred to an LPCVD deposition reactor or module withexposure to the atmosphere. In other words, the preclean process is notan in situ process and native oxide growth on the silicon surfaces ofthe wafer is possible. The LPCVD reactor or module is then utilized toperform the predeposition and conventional nitride deposition process.

With respect to the process using the silicon predeposition, severaldistinct advantages result therefrom. For example, with use of the thinsilicon film on the substrate surface or surfaces, a uniform siliconappearance is apparent at the time of the silicon nitride deposition. Assuch, the nitride nucleation and deposition rate of the silicon nitrideupon the predeposited silicon is substantially the same and notdependant on whether the surface or surfaces are TEOS, silicon, BPSG,etc.

In addition, silicon nitride nucleation occurs faster with the use ofthe predeposited silicon than when no predeposition method is utilized.Such faster nucleation occurs because there is virtually no incubationtime at the start of the silicon nitride deposition method. The thinsilicon predeposited film is similar in nature to the silicon surfacethat would be formed when the silicon is precleaned insitu in a clustertool. Therefore, when using a cluster tool, the advantage of fastersilicon nitride nucleation may not be apparent because there isvirtually no incubation period as no native oxide is allowed to formbetween HF preclean and silicon nitride deposition. However, thepredeposition process used with a cluster tool still provides thebenefit of uniform nucleation and substantially equivalent depositionrates of the silicon nitride on different wafer surfaces or films.

Further, the semiconductor devices fabricated with the silicon nitridedeposition method according to the present invention has improvedelectrical characteristics due to uniform nucleation, substantiallyequivalent deposition rates between different wafer surfaces, and fasternucleation. Such electrical characteristics include, for example, higherbreakdown voltage and greater oxidation resistance compared to siliconnitride deposited by conventional LPCVD techniques.

Moreover, with use of the predeposited silicon and then the depositionof the silicon nitride layer while the wafer is still under vacuum in aconventional LPCVD furnace, no native oxide growth occurs and thebenefits of a cluster tool are achieved without the use of a clustertool. Therefore, the associated cost and lower throughput associatedwith the use of a cluster tool is avoided.

The present invention is beneficial for all thin dielectric applicationsusing silicon nitride. For example, such applications include thedielectrics for memory cells as shown in FIGS. 3A-3C. Further, thepresent invention would also provide improved interface characteristicsfor other thin dielectric applications such as, for example, a gatedielectric. The memory cells illustrated in FIGS. 3A-3C include a planarcell 50, a stack cell 60, and a trench cell 80, respectively.

The planar memory cell 50 of FIG. 3A, includes the silicon nitridedielectric film 56 deposited on the n+-type silicon 54 which serves asthe bottom plate of the capacitor. As shown, the silicon nitride film 56is not only deposited on the n+-type silicon but also is deposited onthe field oxide 55, and TEOS spacer 58. This illustrates the need forsubstantially uniform nucleation and deposition rates over varying typesof surfaces as previously described. The polysilicon region 57 forms thetop plate of the capacitor of the cell. The n+-type silicon 54 andn+-type silicon regions 53 are formed in the p-type silicon substrate52. The other regions, not previously mentioned, used in forming thetransistor of the cell include polysilicon region 59, gate oxide 92, andmetalization 51.

The stack memory cell 60 of FIG. 3B, includes the silicon nitridedielectric film 69 deposited on the polysilicon layer 66 which serves asthe bottom plate of the capacitor of the memory cell. As shown, thesilicon nitride film 69 is not only deposited on the polysilicon layer66 but also is deposited on the field oxide 64, and TEOS layer 67. This,once again, illustrates the need for substantially uniform nucleationand deposition rates over varying types of surfaces as previouslydescribed. The polysilicon region or layer 70 forms the top plate of thecapacitor of the cell. The n+-type silicon region 63 and n+-type siliconregion 62 are formed in the p-type silicon substrate 61. The otherregions, not previously mentioned, used in forming the transistor of ofthe cell include polysilicon region 68, gate oxide 65, and metalization71.

The trench memory cell 80 of FIG. 3C, includes the silicon nitridedielectric film 85 deposited on the n+-type silicon 84 which serves asthe bottom plate of the capacitor. As shown, the silicon nitride film 85is not only deposited on the n+-type silicon but also is deposited onthe field oxide 83, and TEOS film or region 88. This further illustratesthe need for substantially uniform nucleation and deposition rates overvarying types of surfaces as previously described. The polysiliconregion 89 forms the top plate of the capacitor of the cell. The n+-typesilicon region 84 and n+-type silicon region 82 are formed in the p-typesilicon substrate 81. The other regions, not previously mentioned, usedin forming the transistor of the cell include polysilicon region 87,gate oxide 86, and metalization 90.

As indicated above, the method in accordance with the present inventionis not only suitable for the memory cells illustrated above, but can beutilized for any dielectric applications utilizing silicon nitridefilms. As such, the above memory cell configurations are purely forillustration only and are not to be taken as limiting to the presentinvention as defined by the accompanying claims.

Although the invention has been described with particular reference topreferred embodiments thereof, variations and modifications of thepresent invention can be made within a contemplated scope of thefollowing claims as is readily known to one skilled in the art.

What is claimed is:
 1. A silicon nitride deposition method comprisingproviding a substrate surface; predepositing at least a monolayer ofsilicon on at least a portion of the substrate surface; and depositing asilicon nitride layer on the predeposited silicon after completing thesilicon predeposition.
 2. The method according to claim 1, wherein anincubation time for the start of silicon nitride nucleation is decreasedrelative to the incubation time for the start of silicon nitridenucleation when silicon nitride is deposited without predeposition ofsilicon on the substrate surface.
 3. The method according to claim 1,wherein predepositing the at least one monolayer of silicon comprisespredepositing the silicon using one of silane, disilane, silicontetrachloride, dichlorosilane, trichlorosilane.
 4. The method accordingto claim 1, wherein the substrate surface comprises one or morecomponent surfaces that include one or more of tetraethylorthosilicate,borophosphosilicate glass, silicon, polysilicon, other doped silicon orpolysilicon surfaces, other doped oxides, thermal silicon dioxide,chemical vapor deposited silicon dioxide, and plasma enhanced chemicalvapor deposited silicon dioxide.
 5. The method according to claim 1,wherein the substrate surface is moved through air after native oxideremoval to a deposition chamber, and further wherein the silicon ispredeposited in the deposition chamber after which the silicon nitridelayer is deposited in the same deposition chamber.
 6. The methodaccording to claim 1, wherein the method further comprises removingnative oxide from the substrate surface in a cluster tool, and furtherwherein the silicon is predeposited after which the silicon nitridelayer is deposited in the same cluster tool.
 7. The method according toclaim 1, wherein silicon nitride nucleation at the substrate surfacehaving silicon predeposited thereon is performed at a substantiallyequivalent rate independent of the surface type.
 8. The method accordingto claim 1, wherein predepositing the at least a monolayer of siliconcomprises predepositing at least a monolayer of silicon on at least aportion of the substrate surface using dichlorosilane, and furtherwherein depositing the silicon nitride layer comprises depositing asilicon nitride layer on the predeposited silicon using dichlorosilaneand a nitrogen containing component.
 9. A silicon nitride depositionmethod comprising: providing a substrate surface in a depositionchamber; predepositing at least a monolayer of silicon on at least aportion of the substrate surface in the deposition chamber; purging thedeposition chamber; and depositing a silicon nitride layer on at least aportion of the predeposited silicon after purging the depositionchamber.
 10. The method according to claim 9, wherein purging thedeposition chamber comprises purging the deposition chamber with anitrogen containing gas.
 11. The method according to claim 9, whereinpredepositing the at least a monolayer of silicon comprisespredepositing at least a monolayer of silicon on at least a portion ofthe substrate surface using dichlorosilane, and further whereindepositing the silicon nitride layer comprises depositing a siliconnitride layer on at least a portion of the predeposited silicon usingdichlorosilane and a nitrogen containing component.
 12. The methodaccording to claim 9, wherein an incubation time for the start ofsilicon nitride nucleation is decreased relative to the incubation timefor the start of silicon nitride nucleation when silicon nitride isdeposited without predeposition of silicon on the substrate surface. 13.The method according to claim 9, wherein the at least a portion of thesubstrate surface comprises one or more component surfaces that includeone or more of tetraethylorthosilicate, borophosphosilicate glass,silicon, polysilicon, other doped silicon or polysilicon surfaces, otherdoped oxides, thermal silicon dioxide, chemical vapor deposited silicondioxide, and plasma enhanced chemical vapor deposited silicon dioxide.14. The method according to claim 13, wherein silicon nitride nucleationat the substrate surface having silicon predeposited thereon isperformed at a substantially equivalent rate independent of the surfacetype.
 15. The method according to claim 9, wherein the substrate surfaceis moved through air after native oxide removal to the depositionchamber.
 16. A silicon nitride deposition method comprising: providing asubstrate surface in a cluster tool; removing native oxide from thesubstrate surface in the cluster tool; predepositing at least amonolayer of silicon on at least a portion of the substrate surface inthe cluster tool; and depositing a silicon nitride layer on at least aportion of the predeposited silicon in the cluster tool.
 17. The methodaccording to claim 16, wherein an incubation time for the start ofsilicon nitride nucleation is decreased relative to the incubation timefor the start of silicon nitride nucleation when silicon nitride isdeposited without predeposition of silicon on the substrate surface. 18.The method according to claim 16, wherein the at least a portion of thesubstrate surface comprises one or more component surfaces that includeone or more of tetraethylorthosilicate, borophosphosilicate glass,silicon, polysilicon, other doped silicon or polysilicon surfaces, otherdoped oxides, thermal silicon dioxide, chemical vapor deposited silicondioxide, and plasma enhanced chemical vapor deposited silicon dioxide.19. The method according to claim 18, wherein silicon nitride nucleationat the substrate surface having silicon predeposited thereon isperformed at a substantially equivalent rate independent of the surfacetype.
 20. A silicon nitride method for use in providing a capacitor, themethod comprising: providing a substrate surface comprising at least asilicon containing electrode surface in a deposition chamber;predepositing at least a monolayer of silicon on at least the electrodesurface; purging the deposition chamber; depositing a silicon nitridelayer on at least a portion of the predeposited silicon after purgingthe deposition chamber; and forming a capacitor dielectric from thedeposited silicon nitride layer.
 21. The method according to claim 20,wherein purging the deposition chamber comprises purging the depositionchamber with a nitrogen containing gas.
 22. The method according toclaim 20, wherein predepositing at least a monolayer of siliconcomprises predepositing at least a monolayer of silicon on at least aportion of the substrate surface using dichlorosilane, and furtherwherein depositing the silicon nitride layer comprises depositing asilicon nitride layer on at least a portion of the predeposited siliconusing dichlorosilane and a nitrogen containing component.
 23. The methodaccording to claim 20, wherein an incubation time for the start ofsilicon nitride nucleation is decreased relative to the incubation timefor the start of silicon nitride nucleation when silicon nitride isdeposited without predeposition of silicon on the substrate surface. 24.The method according to claim 20, wherein the substrate surfacecomprises one or more component surfaces that include one or more oftetraethylorthosilicate, borophosphosilicate glass, silicon,polysilicon, other doped silicon or polysilicon surfaces, other dopedoxides, thermal silicon dioxide, chemical vapor deposited silicondioxide, and plasma enhanced chemical vapor deposited silicon dioxide.25. The method according to claim 24, wherein silicon nitride nucleationat the substrate surface having silicon predeposited thereon isperformed at a substantially equivalent rate independent of the surfacetype.
 26. The method according to claim 28, wherein the substratesurface is moved through air after native oxide removal to thedeposition chamber.
 27. A silicon nitride deposition method for use inproviding a gate dielectric, the method comprising: providing asubstrate surface comprising at least a silicon containing surface in adeposition chamber; predepositing at least a monolayer of silicon on atleast a portion of the silicon containing surface; purging thedeposition chamber; depositing a silicon nitride layer on at least aportion of the predeposited silicon after purging the depositionchamber; forming the gate dielectric from the deposited silicon nitridelayer.
 28. The method according to claim 27, wherein purging thedeposition chamber comprises purging the deposition chamber with anitrogen containing gas.
 29. The method according to claim 27, whereinpredepositing at least a monolayer of silicon comprises predepositing atleast a monolayer of silicon on at least a portion of the substratesurface using dichlorosilane, and further wherein depositing the siliconnitride layer comprises depositing a silicon nitride layer on at least aportion of the predeposited silicon using dichlorosilane and a nitrogencontaining component.
 30. The method according to claim 27, wherein anincubation time for the start of silicon nitride nucleation is decreasedrelative to the incubation time for the start of silicon nitridenucleation when silicon nitride is deposited without predeposition ofsilicon on the substrate surface.
 31. The method according to claim 27,wherein the substrate surface is moved through air after native oxideremoval to the deposition chamber.